Method for the production of cyclic ketones

ABSTRACT

The present invention relates to a process for preparing a cyclic ketone having from 7 to 16 carbon atoms, which comprises at least the steps 
     (a) oxidation of a composition (I) comprising at least one cyclic alkene which has from 7 to 16 carbon atoms and at least one C—C double bond by means of dinitrogen monoxide to give a composition (A), 
     (b) treatment of the composition (A) with at least one base to give a composition (B), 
     (c) hydrogenation of the composition (B) in the presence of at least one catalyst to give a composition (C), 
     (d) purification of the composition (C), comprising at least the steps 
     (di) thermal treatment of the composition (C) with at least one acid or at least one catalyst comprising at least one transition metal, 
     (dii) further purification by a method selected from the group consisting of distillation, extraction and crystallization.

The present invention relates to a process for preparing a cyclic ketonehaving from 7 to 16 carbon atoms, which comprises at least the oxidationof a composition (I) comprising at least one cyclic alkene which hasfrom 7 to 16 carbon atoms and at least one C—C double bond by means ofdinitrogen monoxide to give a composition (A), treatment of thecomposition (A) with at least one base to give a composition (B),hydrogenation of the composition (B) in the presence of at least onecatalyst to give a composition (C) and purification of the composition(C), comprising at least a thermal treatment of the composition (C) withat least one acid or at least one catalyst comprising at least onetransition metal, and further purification by a method selected from thegroup consisting of distillation, extraction and crystallization.

The oxidation of an olefinic compound by means of dinitrogen monoxide toform an aldehyde or a ketone is described, for example, in GB 649,680 orthe equivalent U.S. Pat. No. 2,636,898. In both documents, it isdisclosed in general terms that the oxidation can in principle becarried out in the presence of a suitable oxidation catalyst. The morerecent scientific articles by G. I. Panov et al., “Non-Catalytic LiquidPhase Oxidation of Olefines with Nitrous Oxide. 1. Oxidation ofCyclohexene to Cyclohexanone”, React. Kinet. Catal. Left. Vol. 76, No. 2(2002) pp. 401-405, and K. A. Dubkov et al., “Non-Catalytic Liquid PhaseOxidation of Olefines with Nitrous Oxide. 2. Oxidation of Cyclopenteneto Cyclopentanone”, React. Kinet. Catal. Left. Vol. 77, No. 1 (2002) pp.197-205, likewise describe oxidations of olefinic compounds by means ofdinitrogen monoxide. A scientific article “Liquid Phase Oxidation ofOlefines with Nitrous Oxide to Carbonyl Compounds” by E. V. Starokon etal. in Adv. Synth. Catal. 2004, 346, 268-274, also reports a mechanisticstudy of the oxidation of olefins by means of dinitrogen monoxide in theliquid phase.

The synthesis of carbonyl compounds from olefins using dinitrogenmonoxide is also described in various international patent applications.Thus, WO 03/078370 discloses a process for preparing carbonyl compoundsfrom aliphatic olefins using dinitrogen monoxide. The reaction iscarried out at temperatures in the range from 20 to 350° C. andpressures of from 0.01 to 100 atm. WO 03/078374 discloses acorresponding process for preparing cyclohexanone. According to WO03/078372, cyclic ketones having from 4 to 5 carbon atoms are prepared.According to WO 03/078375, cyclic ketones are prepared from cyclicolefins having from 7 to 20 carbon atoms under these process conditions.WO 03/078371 discloses a process for preparing substituted ketones fromsubstituted olefins. WO 04/000777 discloses a process for reactingdiolefins and polyolefins with dinitrogen monoxide to form thecorresponding carbonyl compounds.

WO 2005/030690 and WO 2005/030689 describe processes for preparingcyclododecanone, in which an oxidation by means of dinitrogen monoxideis carried out in one process step. WO 2005/030690 describes a processfor preparing cyclododecanone by oxidation of 1,5,9-cyclododecatriene(CDT) by means of N₂O to form cyclododeca-4,8-dienone and subsequenthydrogenation of cyclododeca-4,8-dienone to give cyclododecanone.

As an alternative, cyclododecanone, for example, is prepared, forexample, by air oxidation of cyclododecane in the presence of boric acidto form cyclododecyl borate, hydrolysis of the borate to cyclododecanoland subsequent dehydrogenation of the cyclododecanol. Cyclododecaneitself is obtained by complete hydrogenation of cyclododecatriene. Adescription of this industrial process for the synthesis ofcyclododecanone may be found, inter alia, in T. Schiffer, G. Oenbrink,“Cyclododecanol, Cyclododecanon and Laurolactam” in Ullmann'sEncyclopedia of Industrial Chemistry, 6th Edition, 2000, ElectronicRelease, Wiley VCH.

A further process starts out from the epoxidation of cyclododecatriene,with cyclododecanone being obtained from the epoxide after hydrogenationand rearrangement. Such a process is described, for example, in EP 1 018498 A2.

DE 103 44 595 A and DE 103 44 594 A describe processes for preparingcyclododecanone, in which an oxidation by means of dinitrogen monoxideis carried out in one process step.

In all processes, the purity of the crude products without additionalpurification is not sufficient for some applications. Organic compoundshaving oxygen-comprising groups, in particular, are frequently stillcomprised in the products obtained in excessively large amounts.

In the oxidation of olefins by means of dinitrogen monoxide, it ispossible for, for example, aidehydes to be formed as by-products, asdescribed, for example, in Panov et al., Adv. Synth. Catal. (2004) 346,268-274.

This is problematical insofar as cyclic ketones are required in highpurity for various applications. Thus, for example, cyclododecanone isan important intermediate in the preparation of, for example,laurolactam, dodecanedicarboxylic acid and polyamides derived therefrom,for example Nylon 12 or Nylon 6.12. The impurities such as aidehydescomprised in the cyclic ketones can be removed only with difficulty byconventional purification methods such as distillation, extraction orrecrystallization, since the functional groups and the number of carbonatoms are similar. For this reason, a very complicated purification, forexample by multistage distillation or crystallization, is necessary inthese cases. These purification methods are therefore complicated andcostly.

It was therefore an object of the present invention to provide a processby means of which cyclic ketones can be obtained in high purity in asimple manner and at low cost.

A further object of the present invention was to provide a purificationmethod by means of which, in particular, oxygen-comprising organiccompounds can be separated off from the cyclic ketones.

According to the invention, this object is achieved by a process forpreparing a cyclic ketone having from 7 to 16 carbon atoms, whichcomprises at least the steps

-   -   (a) oxidation of a composition (I) comprising at least one        cyclic alkene which has from 7 to 16 carbon atoms and at least        one C—C double bond by means of dinitrogen monoxide to give a        composition (A),    -   (b) treatment of the composition (A) with at least one base to        give a composition (B),    -   (c) hydrogenation of the composition (B) in the presence of at        least one catalyst to give a composition (C),    -   (d) purification of the composition (C), comprising at least the        steps        -   (di) thermal treatment of the composition (C) with at least            one acid or at least one catalyst comprising at least one            transition metal,        -   (dii) further purification by a method selected from the            group consisting of distillation, extraction and            crystallization.

It has surprisingly been found that, in particular, a mixture of cyclicketones with by-products such as cyclic and open-chain aldehydes havingan identical or similar number of carbon atoms can be selectivelydepleted in the by-products by firstly treating the mixture obtainedafter the oxidation with a base, for example with a base at elevatedtemperature, and, after the hydrogenation, treating the mixture obtainedwith an acid or a catalyst comprising at least one transition metal. Forthe purposes of the present invention, the term “depleted” means thatthe ratio of aldehyde to cyclic ketone is reduced and, in particular,the cyclic ketone is essentially not attacked.

Furthermore, the process of the invention makes it possible to improvethe yield of cyclic ketones since the treatment with base and acid orcatalyst comprising transition metal is generally very selective andless product is therefore lost in the subsequent purification bydistillation or crystallization.

For the purposes of the present patent application, the term “treatment”refers to contacting of a composition with the respective compound, i.e.with at least one base in step (b) or with at least one acid or with atleast one catalyst comprising at least one transition metal in step (d).According to the invention, the composition (C) is thermally treatedwith an acid or a catalyst comprising at least one transition metal instep (di).

The process of the invention enables cyclic ketones having a purity of,for example, >99.5% to be obtained. The process of the invention caneasily be combined with existing plants, so that no costly modificationsare necessary. Furthermore, the process of the invention makes itpossible to improve the yield of cyclic ketones since the treatment withbase and acid or catalyst comprising transition metal is generally veryselective and less product is therefore lost.

The reaction in step (a) can generally be carried out using allprocedures in which the olefin and dinitrogen monoxide react with oneanother.

In step (a) of the process of the invention, the cyclic olefin isoxidized by reaction with dinitrogen monoxide. It is possible to use atleast one suitable solvent or diluent for the reaction of the cyclicolefin with dinitrogen monoxide. Such solvents or diluents are, interalia, cyclic alkanes, for example cyclododecane, or cyclododecanone orsaturated aliphatic or aromatic, optionally alkyl-substitutedhydrocarbons. Essentially all customary solvents and/or diluents aresuitable, provided that they have neither a C—C double bond nor a C—Ctriple bond nor an aldehyde group.

In general, the addition of a solvent or diluent is not necessary in thereaction of the cyclic olefin with dinitrogen monoxide.

The temperatures in the reaction of the cyclic olefin with dinitrogenmonoxide are preferably in the range from 140 to 350° C., morepreferably in the range from 180 to 320° C. and particularly preferablyin the range from 200 to 300° C.

It is possible to carry out the reaction of the cyclic olefin withdinitrogen monoxide at two or more temperatures or in two or moretemperature ranges which are each within the abovementioned limits.Temperature changes during the course of the reaction can be carried outcontinuously or discontinuously.

The pressures in the reaction of the cyclic olefin with dinitrogenmonoxide are preferably above the autogenous pressure of the startingmaterial or product mixture at the selected reaction temperature or theselected reaction temperatures. The pressures are preferably in therange from 1 to 1000 bar, more preferably in the range from 40 to 300bar and particularly preferably in the range from 50 to 200 bar.

The pressure in the reaction vessel, preferably in a least one tubereactor, is generally greater than or equal to, preferably greater than,the autogenous pressure of the starting material mixture or the productmixture at the selected reaction temperature or the selected reactiontemperatures in the reaction vessel. In general, the reaction pressuresare in the range from 1 to 14 000 bar, preferably in the range from theautogenous pressure to 3000 bar, particularly preferably in the rangefrom the autogenous pressure to 1000 bar and very particularlypreferably in the range from the autogenous pressure to 325 bar, forexample from 50 to 200 bar.

It is possible to carry out the reaction of the cyclic olefin withdinitrogen monoxide at two or more pressures or in two or more pressureranges which are each within the abovementioned limits. Pressure changesduring the course of the reaction can be carried out continuously ordiscontinuously.

The reactors which can be used for the reaction of the cyclic olefinwith dinitrogen monoxide are not subject to any particular restrictions.In particular, the reaction can be carried out batchwise orcontinuously. Accordingly, it is possible to use, for example, at leastone CSTR (continuous stirred tank reactor) having at least one internaland/or at least one external heat exchanger, at least one tube reactor,at least one shell-and-tube reactor or at least one loop reactor asreactors. It is likewise possible to configure at least one of thesereactors so that it has at least two different zones. Such zones candiffer, for example, in terms of reaction conditions such as thetemperature or the pressure and/or in terms of the geometry of the zone,for example the volume or cross section. If the reaction is carried outin two or more reactors, it is possible to use two or more identicaltypes of reactor or at least two different types of reactor.

The reaction of the cyclic olefin with dinitrogen monoxide is preferablycarried out in a single reactor. For example, preference is given to acontinuous reaction.

The residence time of the reaction mixture in the at least one reactorin the reaction of the cyclic olefin with dinitrogen monoxide isgenerally in the range up to 20 hours, preferably in the range from 0.1to 20 hours, more preferably in the range from 0.2 to 15 hours andparticularly preferably in the range from 0.25 to 10 hours.

In the feed supplied to the reaction of dinitrogen monoxide with thecyclic olefin, the molar ratio of dinitrogen monoxide to the cyclicolefin is generally in the range from 0.05 to 4, preferably in the rangefrom 0.06 to 1, more preferably in the range from 0.07 to 0.5 andparticularly preferably in the range from 0.1 to 0.4.

The reaction of the cyclic olefin with dinitrogen monoxide can becarried out so that a conversion of the cyclic olefin in the range up to50%, preferably in the range from 5 to 30% and particularly preferablyin the range from 10 to 20%, is achieved at a very high selectivity tothe cyclic ketone. The selectivity, based on the cyclic ketone, isgenerally at least 90%, preferably at least 92.5% and particularlypreferably at least 93%.

According to the invention, it is in principle possible to react anycyclic olefin having from 7 to 16 carbon atoms or any mixture of two ormore different cyclic olefins having from 7 to 16 carbon atoms withdinitrogen monoxide. Suitable olefins are, for example, cyclic olefinshaving one or more C—C double bonds.

According to the invention, the cyclic olefin particularly preferablyhas 2, 3 or 4 C—C double bonds.

For the purposes of the invention, the cyclic olefin preferably has atleast two C—C double bonds.

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the cyclic alkene has three C—C doublebonds.

Further preference is given to cyclic olefins having one or more C—Cdouble bonds, for example cycloheptene, cyclooctene, cyclodecene,cycloundecene, cyclododecene, 1,5-cyclooctadiene, 1,5-cyclododecadieneor 1,5,9-cyclododecatriene.

Particular preference is given to using cyclododecene or1,5,9-cyclododecatriene as olefin. Mention may here be made of, forexample, 1,5,9-cyclododecatrienes, for examplecis,trans,trans-1,5,9-cyclododecatriene orcis,cis,trans-1,5,9-cyclododecatriene orall-trans-1,5,9-cyclododecatriene.

Preference is given to using cis,trans,trans-1,5,9-cyclododecatriene ascyclododecatriene.

In a preferred embodiment, the present invention therefore provides aprocess for preparing a ketone as described above, wherein the olefin isselected from the group consisting of cyclododecene andcyclododecatriene, in particular 1,5,9-cyclododecatriene.

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the cyclic alkene is cyclododecatriene.

In a preferred embodiment of the present invention, cyclododecatrienes,preferably 1,5,9-cyclododecatriene, are used as cyclic olefin comprisedin the composition (I).

The present invention therefore also provides, according to a furtherembodiment, a process as described above for preparing a cyclic ketonehaving from 7 to 16 carbon atoms, wherein the cyclic olefin is acyclododecatriene.

Cyclododecatriene is preferably obtained by trimerization of butadiene.

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the cyclic olefin is cyclododecatriene whichhas been prepared from butadiene by means of trimerization.

1,5,9-cyclododecatrienee can be prepared, for example, by trimerizationof pure 1,3-butadiene, as described, for example, in T. Schiffer, G.Oenbrink, “Cyclododecatriene, Cyclooctadiene, and 4-Vinylcyclohexene”,Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition (2000),Electronic Release, Wiley VCH. In this process, for example,cis,trans,trans-1,5,9-cyclododecatriene,cis,cis,trans-1,5,9-cyclododecatriene andall-trans-1,5,9-cyclododecatriene are formed in the trimerization in thepresence of Ziegler catalysts, as described, for example, in H. Weber etal. “Zur Bildungsweise von cis,trans,trans-Cyclododecatriene-(1,5,9)mittels titanhaltiger Katalysatoren” in: Liebigs Ann. Chem. 681 (1965),pp. 10-20. Cyclododecatriene can be prepared by trimerization of1,3-butadiene using a titanium catalyst.

While all suitable titanium catalysts can in principle be used for thetrimerization, the titanium tetrachloride/ethylaluminum sesquichloridecatalyst described in the article by Weber et al. is particularlyuseful.

The butadiene used for the trimerization particularly preferably has apurity determined by gas chromatography of at least 99.6% and morepreferably at least 99.65%. The 1,3-butadiene used particularlypreferably comprises no 1,2-butadiene and no 2-butyne within thedetection limits.

This trimerization generally gives mixtures comprising at least 95% byweight, preferably at least 96% by weight and more preferably at least97% by weight of cis,trans,trans-1,5,9-cyclododecatriene. For example,the mixtures particularly preferably comprise about 98% by weight ofcis,trans,trans-1,5,9-cyclododecatriene.

This mixture comprising cis,trans,trans-1,5,9-cyclododecatriene can beused as such for the reaction in step (a). It is likewise possible toseparate off the cis,trans,trans-1,5,9-cyclododecatriene from themixture by means of at least one suitable method, for example preferablyby means of at least one distillation, and use it in the reaction instep (a).

For the purposes of the present invention, it is in principle possibleto react any cyclododecatriene or any mixture of two or more differentcyclododecatrienes with dinitrogen monoxide in step (a). Examples whichmay be mentioned here are, inter alia, 1,5,9-cyclododecatrienes, forexample, cis,trans,trans-1,5,9-cyclododecatriene orcis,cis,trans-1,5,9-cyclododecatriene orall-trans-1,5,9-cyclododecatriene.

In a very particularly preferred embodiment of the process of theinvention, an isomer mixture comprising predominantlycis,trans,trans-1,5,9-cyclododecatriene,trans,trans,trans-1,5,9-cyclododecatriene orcis,cis,trans-1,5,9-cyclododecatriene as cyclododecatriene. Preferenceis given to using an isomer mixture comprising more than 60% by weight,based on the isomer mixture, of cis,trans,trans-1,5,9-cyclododecatriene,more preferably more than 70% by weight, in particular more than 80% byweight, particularly preferably more than 90% by weight, for examplemore than 91% by weight, more than 92% by weight, more than 93% byweight, more than 94% by weight, more than 95% by weight, more than 96%by weight, more than 97% by weight or more than 98% by weight.

In general, the reaction according to the invention ofcis,trans,trans-1,5,9-cyclododecatriene with dinitrogen monoxide in step(a) results in a cyclododeca-4,8-dienone isomer mixture comprising atleast two of the isomers cis,trans-cyclododeca-4,8-dienone,trans,cis-cyclododeca-4,8-dienone andtrans,trans-cyclododeca-4,8-dienone. According to the invention,preference is given to an isomer mixture in which the trans,cis isomerand cis,trans isomer are formed in approximately equal amounts and thetrans,trans isomer is formed in only minor amounts compared to the othertwo isomers being obtained. An example of a typical isomer mixtureaccordingly comprises the isomers in molar ratios of about 1:1:0.08.

The reaction according to the invention of composition (I) comprisingcyclododecatriene with dinitrogen monoxide in step (a) generally gives,as composition (A), a mixture comprising cyclododecadienone, preferablycyclododeca-4,8-dienone, and possibly unreacted starting material and/orpossibly at least one by-product. Depending on the further use and/orwork-up, the cyclododecadienone, preferably cyclododeca-4,8-dienone, canbe separated off from this mixture.

The cyclododeca-4,8-dienone can be separated off from this mixture by atleast one suitable method. Preference is here given to separation bydistillation. The distillation here is generally carried out at apressure in the range from 0.001 to 2 bar, preferably in the range from0.01 to 1 bar and particularly preferably in the range from 0.02 to 0.5bar.

In a particularly preferred embodiment of the process of the invention,a composition (b) comprising cyclododeca-4,8-dienone is hydrogenated instep (c) to give a composition (C) comprising cyclododecanone.

The reaction of the cyclic olefin with dinitrogen monoxide can inprinciple be carried out in the presence of a catalyst, but also withoutaddition of a catalyst.

For the purposes of the present invention, dinitrogen monoxide can beused in pure form or in the form of a gas mixture comprising dinitrogenmonoxide.

It is in principle possible to use any gas mixture comprising dinitrogenmonoxide in step (a) of the process of the invention. It is alsopossible, according to the invention, to purify or concentrate the gasmixture comprising dinitrogen monoxide before it is used in the reactionin step (a). A suitable purification method comprises, for example,absorption of the gas mixture in an organic solvent or water, desorptionof the gas mixture from the laden organic solvent or the laden water andsetting of the content of nitrogen oxides NO_(x) in the gas mixture tonot more than from 0.01 to 0.001% by volume, based on the total volumeof the gas mixture. Such a process is described, for example, in DE 102004 046 167.8, whose relevant contents are fully incorporated byreference into the present patent application.

The gas mixture comprising dinitrogen monoxide which is used can inprinciple originate from any source. In particular, it is possible touse the offgas of a process as described in DE 10 2004 046 167.8 asdinitrogen monoxide source.

The term “gas mixture” as used in the context of the present inventionrefers to a mixture of two or more compounds which are in the gaseousstate at ambient pressure and ambient temperature. At a differenttemperature or different pressure, the gas mixture can also be inanother state of matter, for example liquid, and will for the purposesof the present invention continue to be referred to as gas mixture.

According to the invention, it is possible to use a mixture of variousoffgases.

In a further preferred embodiment of the present invention, the at leastone offgas comprising dinitrogen monoxide originates from an adipic acidplant, a dodecanedioic acid plant, a hydroxylamine plant and/or a nitricacid plant, with the latter in turn preferably being operated using atleast one offgas from an adipic acid plant, a dodecanedioic acid plantor a hydroxylamine plant.

According to the invention, the gas mixture can be used in gaseous form.However, it is also possible firstly to treat the gas mixture comprisingdinitrogen monoxide so that the gas mixture or dinitrogen monoxide ispresent in liquid or supercritical form and then use it. The gas mixtureor dinitrogen monoxide can be liquefied by appropriate choice of thepressure or temperature. It is likewise possible, for the purposes ofthe present invention, to dissolve the gas mixture in a solvent.

According to the invention, the composition (I) usually comprises thecyclic olefin in an amount of more than 80% by weight, preferably from85 to 99.999% by weight, in particular from 90 to 99.99% by weight,particularly preferably from 92 to 99.9% by weight, for example from 95to 99.8% by weight. The composition (I) can usually comprise furthercompounds, in particular organic compounds, in addition to the cyclicolefin.

The composition (I) can comprise, for example, vinylcyclohexene,cyclooctadiene and, for example, bicyclic isomers of1,5,9-cyclododecatriene as organic compounds. It is also possible fortraces of C₁₆ components, C₂₄ components or higher oligomers to becomprised.

In the reaction in step (a) of the process of the invention, the cyclicolefin comprised in the composition (I) is oxidized by means ofdinitrogen monoxide. This gives a composition (A) comprising at leastone cyclic ketone.

The composition (A) in the context of the present invention comprises atleast one cyclic ketone having from 7 to 16 carbon atoms. According tothe invention, the composition (A) comprises the cyclic ketone in anamount of more than 5% by weight, preferably more than 10% by weight,more preferably from 10 to 90% by weight, in particular from 11 to 50%by weight, particularly preferably from 12 to 40% by weight, veryparticularly preferably from 13 to 30% by weight, for example from 14 to20% by weight or from 15 to 18% by weight. The composition (A) usuallycomprises further compounds, in particular organic compounds, forexample unreacted starting material or organic compounds havingoxygen-comprising groups, for example alcohols, aldehydes or epoxides,in addition to the cyclic olefin. Here, the organic compounds can have,in particular, the same number of carbon atoms as the cyclic ketonecomprised in the composition (A).

The composition (A) can be used directly in step (b) of the process ofthe invention. However, it is also possible to subject the composition(A) to an intermediate treatment before step (b). For example, unreactedstarting material can be separated off from the composition (A). It islikewise possible for by-products of the oxidation, for examplediketones, to be separated off. According to the invention, unreactedstarting material and diketones can preferably be separated off. Theseparation can, for example, be carried out by distillation in one ormore columns, preferably in at least two columns.

According to the invention, the composition (A) is treated with at leastone base in step (b). The process conditions for the treatment can bevaried within a wide range, as long as it is ensured that theconcentration of at least one aldehyde is reduced.

According to the invention, the amount of the aldehyde is reduced inthis treatment while the cyclic ketone is essentially not attacked.Here, open-chain aldehydes are, according to the invention, preferablydegraded to an extent of more than 90%, in particular more than 95% andparticularly preferably 99.99%. Cyclic aldehydes having an exocyclicaldehyde group are preferably degraded to an extent of up to 30%, inparticular up to 35% and particularly preferably up to 40%. According tothe invention, the cyclic ketone is degraded only to an extent of from0.5 to 2.0%, preferably from 0.75 to 1.75%, in particular from 1.0 to1.5%.

In general, the treatment with base is continued until at least 90%,preferably at least 95%, of at least one aldehyde, preferably at leastone open-chain aldehyde, have been reacted.

According to the invention, the treatment with at least one base in step(b) is preferably carried out for a period of from 1 minute to 10 hours,in particular from 5 minutes to 5 hours, particularly preferably from 10to 60 minutes, more preferably from 20 to 50 minutes.

The treatment in the process of the invention can, in particular, becarried out at a temperature of from 100 to 250° C., preferably from 110to 220° C., particularly preferably from 120 to 200° C., more preferablyfrom 150 to 190° C.

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the treatment in step (b) is carried out ata temperature of from 100 to 250° C. for a period of from 1 minute to 10hours.

All possible types of reactor are suitable for the treatment with thebase. For a continuous reaction, preference is given to using reactorshaving tube characteristics, e.g. tube reactors, cascades of stirredvessels or comparable reactors. For a discontinuous reaction (batchprocess), simple stirred vessels are well suited. The reactionpreferably proceeds essentially homogeneously in the liquid phase.

The treatment in step (b) preferably comprises two substeps (b1) and(b2), with the composition (A) being treated with at least one base instep (b1) and the base being separated off in step (b2).

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the step (b) comprises the substeps (b1) and(b2):

-   -   (b1) treatment of the composition (A) with at least one base    -   (b2) removal of the base.

The removal of the base in (b2) can be carried out by all customarymethods, for example by distillation. Particularly when NaOH or KOH isused as base, the removal is preferably effected by evaporation, forexample in the form of a falling film evaporator, a wiped filmevaporator or a helical tube evaporator, or by extraction of the base,for example with water.

For the purposes of the present invention, it is in principle possibleto use all suitable bases. Preference is given to using organic orinorganic bases whose conjugate acid has a pK_(a) relatively to waterof >9. For the purposes of the present invention, preference is givento, for example, trialkylamines, alkali metal alkoxides or alkalineearth metal alkoxides and tetraalkylammonium, alkali metal or alkalineearth metal hydroxides. Very particular preference is given to sodiumhydroxide and potassium hydroxide.

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the base is selected from among sodiumhydroxide and potassium hydroxide.

The base can, according to the invention be used either as a puresubstance or as a solution. Liquid bases are preferably used withoutaddition of a solvent. Solid bases are preferably used as a solution.The conjugate acid is preferably used as solvent. The particularlypreferred bases NaOH and KOH are preferably used as concentrated aqueoussolution. A base used as a solution preferably has a concentration of atleast 25% by weight, in particular at least 40% by weight, particularlypreferably about 50% by weight.

The amount of base used in step (b) can be varied within a wide range.It is possible to use from 0.01 to 5 mol of base/mol of aldehyde.Preference is given to using from 0.05 to 2 mol of base/mol of aldehyde.Particular preference is given to using from 0.1 to 1 mol of base/mol ofaldehyde.

The treatment with the base is carried out in the temperature range from100 to 250° C. The reaction is preferably carried out in the range from110 to 220° C. The reaction is particularly preferably carried out inthe range from 150 to 190° C. The duration of the treatment isdetermined by the temperature selected, the type and amount of base andby the desired degree of depletion for the aldehydes. The conditions arepreferably selected so that the duration of the treatment is from 1minute to 10 hours, for example from 10 minutes to 5 hours, inparticular from 20 minutes to 4 hours, preferably from 30 minutes to 3hours, more preferably from 40 minutes to 2 hours, particularlypreferably from 50 minutes to 1.5 hours.

In a preferred embodiment, the treatment with the base is carried out ata temperature of from 160 to 18° C. for a time of from 30 to 40 minutes.The treatment is preferably carried out using 0.1 to 0.15% by weight ofsodium hydroxide, based on the total composition. In a particularlypreferred embodiment, the treatment with the base is carried out at atemperature of from 160 to 185° C. for a time of from 30 to 40 minutesusing from 0.1 to 0.15% by weight of sodium hydroxide, based on thetotal composition.

According to the invention, the composition (B) comprises at least onecyclic ketone. The composition (B) usually comprises the cyclic ketonein an amount of more than 40% by weight, preferably from 50 to 99.9% byweight, in particular from 55 to 99% by weight, particularly preferablyfrom 60 to 95% by weight.

The composition (B) can, for example, also comprise further organiccompounds, for example 1,5,9-cyclododecatriene,1,2-epoxycyclododeca-5,9-diene, cycloundecadiene carbaldehyde,C₁₂-diketones or traces of oligomeric compounds. The composition (B) cancomprise, for example, 1,5,9-cyclododecatriene in amounts of from 0.2 to0.6% by weight, 1,2-epoxycyclododeca-5,9-diene in amounts of from 0.01to 0.1% by weight, cycloundecadiene carbaldehyde in amounts of from 0.5to 1.2% by weight, C₁₂-diketone in amounts of from 0.5 to 3.0% by weightor traces of oligomeric compounds.

After at least part of the base has been separated off, the compositioncan be subjected to further intermediate treatments.

The cyclic olefin used in the process of the present inventionpreferably has at least two C—C double bonds, i.e., for example, 2, 3, 4or 5.

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the cyclic olefin has at least two C—Cdouble bonds.

If the cyclic olefin has more than one C—C double bond, preference isgiven to only one of the C—C double bonds being oxidized in theoxidation in step (a) of the process of the invention. According to theinvention, the cyclic ketone comprised in the composition (A) has atleast one C—C double bond, particularly preferably at least two doublebonds.

According to the invention, the oxidation in step (a) is carried out sothat very little backmixing, particularly preferably no backmixing,occurs in the reaction.

After the oxidation in step (a), the at least one remaining C—C doublebond of the cyclic ketone comprised in the composition (A) orcomposition (B) is, after step (b), reacted further in step (c)according to the invention.

According to the invention, the composition (B) obtained in step (b) ishydrogenated in step (c).

In the hydrogenation in step (c), the cyclic ketone comprised incomposition (B) is hydrogenated. This gives a composition (C) comprisinga cyclic ketone which preferably no longer has any C—C double bond.

The composition (C) usually comprises the cyclic ketone in an amount ofmore than 80% by weight, preferably from 85 to 99.9% by weight, inparticular from 88 to 99.9% by weight, particularly preferably from 90to 99.6% by weight, more preferably from 92 to 99.0% by weight. Thecomposition (C) usually comprises further compounds, in particularorganic compounds, preferably ones having oxygen-comprising groups, forexample alcohols, aidehydes or epoxides, in addition to the cyclicketone. The organic compounds can, in particular, have the same numberof carbon atoms as the cyclic ketone comprised in the composition (C).

The secondary components are, in particular, comprised in amounts ofless than 20% by weight, in particular less than 15% by weight,particularly preferably less than 12% by weight, in the composition (C).For example, the secondary components are comprised in an amount of from0.001 to 10% by weight, in particular from 0.1 to 9% by weight,preferably from 0.5 to 5% by weight, particularly preferably from 1 to4% by weight.

According to the present invention, the composition (B) can be useddirectly in step (c). However, it is likewise possible for the purposesof the present invention for the composition (B) firstly to be treatedand then be used in step (c).

All suitable catalysts can be used for the hydrogenation in step (c). Inparticular, it is possible to use at least one homogeneous catalyst orat least one heterogeneous catalyst or both at least one homogeneouscatalyst and at least one heterogeneous catalyst.

The catalysts which can be used preferably comprise at least one metalof transition group 7, 8, 9, 10 or 11 of the Periodic Table of theElements. The catalysts which can be used according to the inventionmore preferably comprise at least one element, selected from the groupconsisting of Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu and Au. Inparticular, the catalysts which can be used according to the inventioncomprise at least one element selected from the group consisting of Fe,Ni, Pd, Pt and Cu. The catalysts which can be used according to theinvention particularly preferably comprise Pd, Pt, Ru or Ni.

Suitable homogeneous catalysts are, for example, ones comprising atleast one element of transition group 8, 9 or 10. Further preference isgiven to homogeneous catalysts comprising Ru, Rh, Ir and/or Ni. Exampleswhich may be mentioned are RhCl(TTP)₃ and RU₄H₄(CO)₁₂. Particularpreference is given to homogeneous catalysts which comprise Ru. Forexample, use is made of homogeneous catalysts as described in U.S. Pat.No. 5,180,870, U.S. Pat. No. 5,321,176, U.S. Pat. No. 5,177,278, U.S.Pat. No. 3,804,914, U.S. Pat. No. 5,210,349 U.S. Pat. No. 5,128,296, USB 316,917 and in D. R. Fahey in J. Org. Chem. 38 (1973) pp. 80-87, whoserelevant disclosure is fully incorporated by reference into the presentpatent application. Such catalysts are, for instance, (TPP)₂(CO)₃Ru,[Ru(CO)₄]₃, (TPP)₂Ru(CO)₂Cl₂, (TPP)₃(CO)RuH₂, (TPP)₂(CO)₂RuH₂,(TPP)₂(CO)₂RuClH or (TPP)₃(CO)RuCl₂.

Another suitable catalyst is, in particular, at least one heterogeneouscatalyst, in the case of which at least one of the abovementioned metalscan be used as metal as such, as Raney catalyst and/or applied to acustomary support. Preferred support materials are, for instance,activated carbons or oxides such as aluminum oxides, silicon oxides,titanium oxides or zirconium oxides. Mention may likewise be made of,inter alia, bentonites as support materials. If two or more metals areused, these can be present separately or as an alloy. Here, it ispossible to use at least one metal as such and at least one other metalas Raney catalyst or at least one metal as such and at least one othermetal applied to at least one support, or at least one metal as Raneycatalyst and at least one other metal applied to at least one support orat least one metal as such and at least one other metal as Raneycatalyst and at least one other metal applied to at least one support.

The catalysts used can, for example, also be precipitated catalysts.Such catalysts can be produced by precipitating their catalyticallyactive components from their salt solutions, in particular from thesolutions of their nitrates and/or acetates, for example by addition ofsolutions of alkali metal and/or alkaline earth metal hydroxides and/orcarbonates, for example as sparingly soluble hydroxides, hydratedoxides, basic salts or carbonates, subsequently drying the precipitatesobtained and then converting these by calcination at generally from 300to 700° C., in particular from 400 to 600° C., into the correspondingoxides, mixed oxides and/or mixed-valence oxides which are reduced bytreatment with hydrogen or hydrogen-comprising gases in the range ofgenerally from 50 to 700° C., in particular from 100 to 400° C., to therespective metals and/or oxidic compounds having a lower oxidation stateand converted into the actual catalytically active form. The reductionis generally continued until no more water is formed. In the productionof precipitated catalysts which comprise a support material, theprecipitation of the catalytically active components can be carried outin the presence of the respective support material. The catalyticallyactive components can advantageously be precipitated simultaneously withthe support material from the respective salt solutions.

Preference is given to using hydrogenation catalysts which comprise themetals or metal compounds which catalyze the hydrogenation deposited ona support material.

Apart from the abovementioned precipitated catalysts which comprise asupport material in addition to the catalytically active components,support materials in which the catalytic hydrogenation-active componenthas been applied to a support material, for example by impregnation, arealso generally suitable for the process of the invention.

The manner in which the catalytically active metal is applied to thesupport is generally not critical and the application can be effected ina variety of ways. The catalytically active metals can, for example, beapplied to the support materials by impregnation with solutions orsuspensions of the salts or oxides of the respective elements, dryingand subsequent reduction of the metal compounds to the respective metalsor compounds having a lower oxidation state by means of a reducingagent, preferably hydrogen or complex hydrides. Another possible way ofapplying the catalytically active metals to the supports is toimpregnate the supports with solutions of salts which are easilydecomposed thermally, for example nitrates or complexes which are easilydecomposed thermally, for example carbonyl or hydrido complexes of thecatalytically active metals, and to heat the support which has beenimpregnated in this way to temperatures in the range from 300 to 600° C.in order to thermally decompose the absorbed metal compounds. Thisthermal decomposition is preferably carried out under a protective gasatmosphere. Suitable protective gases are, for example, nitrogen, carbondioxide, hydrogen or the noble gases. Furthermore, the catalyticallyactive metals can be applied to the catalyst support by vapor depositionor by flame spraying. The content of the catalytically active metals inthese supported catalysts is in principle not critical for the successof the process of the invention. In general, higher contents ofcatalytically active metals in these supported catalysts lead to higherspace-time yields than do lower contents. In general, supportedcatalysts whose content of catalytically active metals is in the rangefrom 0.1 to 90% by weight, preferably in the range from 0.5 to 40% byweight, based on the total weight of the catalyst, are used. Since thesecontent figures are based on the total catalyst including supportmaterial but the various support materials have very different specificgravities and specific surface areas, it is also conceivable that valuesbelow and above these figures can be used without this having an adverseeffect on the result of the process of the invention. Of course, aplurality of catalytically active metals can also be applied to therespective support materials. Furthermore, the catalytically activemetals can be applied to the support by the process of DE-A 25 19 817,EP 1 477 219 A1 or EP 0 285 420 A1. In the catalysts according to theabovementioned documents, the catalytically active metals are present asalloys which are produced by thermal treatment and/or reduction of, forexample, the support material which has been impregnated with a salt orcomplex of the abovementioned metals.

The activation of both the precipitated catalysts and the supportedcatalysts can also be carried out in situ at the beginning of thereaction by means of the hydrogen present. Preference is given toactivating these catalysts separately before they are used.

As support materials, it is generally possible to use the oxides ofaluminum and titanium, zirconium dioxide, silicon dioxide, clay mineralssuch as montmorillonites, silicates such as magnesium or aluminumsilicates, zeolites such as the structural types ZSM-5 or ZSM-10, oractivated carbon. Preferred support materials are aluminum oxides,titanium dioxides, silicon dioxide, zirconium dioxide and activatedcarbon. It is of course also possible to use mixtures of various supportmaterials as supports for catalysts which can be used in the process ofthe invention.

According to the invention, very particularly preferred catalysts areones which comprise Ni, Pt and/or Pd and are applied to a support. Verypreferred supports are or comprise activated carbon, aluminum oxide,titanium dioxide and/or silicon dioxide.

The at least one heterogeneous catalyst can, for example, be used assuspended catalyst and/or as fixed-bed catalyst.

If, for example, the hydrogenation in step (c) of the process of theinvention is carried out using at least one suspended catalyst, thehydrogenation is preferably carried out in at least one stirred reactoror in at least one bubble column or in at least one packed bubble columnor in a combination of two or more identical or different reactors.

For the present purposes, the term “different reactors” refers both todifferent types of reactor and to reactors of the same type whichdiffer, for example, in terms of their geometry, for example theirvolume and/or their cross section, and/or in terms of the hydrogenationconditions in the reactors.

If, for example, the hydrogenation in step (c) of the process of theinvention is carried out using at least one fixed-bed catalyst, thenpreference is given to using at least one tube reactor such as at leastone shaft reactor and/or at least one shell-and-tube reactor, with asingle reactor being able to be operated in the upflow mode or thedownflow mode. When two or more reactors are used, it is possible tooperate at least one in the upflow mode and at least one in the downflowmode.

If, for example, a heterogeneous catalyst is used as suspended catalystin the hydrogenation, this is, for the purposes of the presentinvention, preferably separated off by means of at least one filtrationstep. The catalyst which is then separated off in this way can berecirculated to the hydrogenation or passed to at least one otherdesired process. It is likewise possible to work up the catalyst, forexample in order to recover the metal comprised in the catalyst.

If, for example, a homogeneous catalyst is used in the hydrogenation instep (c), this is, for the purposes of the present invention, preferablyseparated off by means of at least one distillation step. Thisdistillation can be carried out using one or two or more distillationcolumns. The catalyst which is then separated off in this way can berecirculated to the hydrogenation or be passed to at least one otherdesired process. It is likewise possible to work up the catalyst, forexample in order to recover the metal comprised in the catalyst.

Before use in any desired process, for example before recirculation tothe process of the invention, both the at least one homogeneous catalystand the at least one heterogeneous catalyst can, if necessary, beregenerated by means of at least one suitable process.

The heat can be removed from the reactor used according to the inventioneither internally, for example by means of cooling coils, and/orexternally, for example by means of at least one heat exchanger. If, forexample, at least one tube reactor is preferably used for thehydrogenation, the reaction mixture is preferably conveyed through anexternal circuit into which the heat removal is integrated.

If, in a preferred embodiment of the process of the invention, thehydrogenation is carried out continuously, further preference is givento using at least two reactors, more preferably at least two tubereactors, more preferably at least two tube reactors connected in seriesand particularly preferably precisely two tube reactors connected inseries. The hydrogenation conditions in the reactors used can in eachcase be identical or different and are in each case in theabove-described ranges.

If the hydrogenation in step (c) is carried out over at least onesuspended catalyst, the residence time is generally in the range from0.05 to 50 hours, for example in the range from 0.5 to 50 hours,preferably in the range from 1 to 30 hours and particularly preferablyin the range from 1.5 to 25 hours, very particularly preferably in therange from 1.5 to 10 hours. Here, it is immaterial whether a mainreactor and an after-reactor or additionally further reactors are usedaccording to the invention. In all these embodiments, the totalresidence time is within the abovementioned ranges.

If the hydrogenation in the process of the invention is carried outcontinuously over at least one fixed-bed catalyst, the space velocityover the catalyst (kg of feed/liter of catalyst×h) is generally in therange from 0.03 to 20, preferably in the range from 0.05 to 5 andparticularly preferably in the range from 0.1 to 2. It is immaterialwhether a main reactor and an after-reactor or additionally furtherreactors are used according to the invention. In all these embodiments,the total space velocity is within the abovementioned ranges.

In general, the hydrogenation temperature in the main reactor is in therange from 0 to 350° C., preferably in the range from 20 to 300° C.,more preferably in the range from 50 to 250° C. and particularlypreferably in the range from 80 to 220° C.

In the hydrogenation according to the invention, the hydrogen pressurein the main reactor is generally in the range from 1 to 325 bar,preferably in the range from 5 to 300 bar, more preferably in the rangefrom 10 to 250 bar and particularly preferably in the range from 15 to150 bar.

In the hydrogenation according to the invention in step (c), it ispossible to use at least one suitable solvent or diluent. As solvents ordiluents, mention may basically be made of all solvents and diluentswhich are not hydrogenated or reacted in another way under thehydrogenation conditions, e.g. alcohols, ethers, hydrocarbons, water,aromatics or ketones, in particular toluene or cyclododecane.

In a preferred embodiment of the process of the invention, thehydrogenation in step (c) is carried out without addition of a solventor diluent.

According to the invention, the composition (C) can be used directly instep (d). However, it is also possible for the composition (C) to besubjected to an intermediate treatment prior to step (d).

The process of the invention further comprises step (d) comprising thesteps (di) and (dii). In step (di), the composition (C) is treatedthermally with an acid or with a catalyst comprising at least onetransition metal. In step (dii), the composition (C) which has beentreated in this way is purified further by distillation, extractionand/or crystallization. The distillation, extraction and/orcrystallization can be carried out by all customary methods known tothose skilled in the art.

Suitable solvents for the crystallization of step (dii) are, forexample, alcohols, ethers, hydrocarbons, aromatic hydrocarbons, ketones,preferably toluene, xylene, methanol, ethanol, propanol, butanol,acetone, diethyl ketone or methyl tert-butyl ether. According to theinvention, it is likewise possible for no solvent to be used but insteada melt crystallization to be carried out.

The purification by distillation can be carried out in one or morecolumns. It is preferably carried out at pressures of from 1 to 2000mbar. Particularly in the case of cyclic ketones having more than 8carbon atoms, preference is given to pressures of from 5 to 500 mbar,particularly preferably from 10 to 200 mbar. The temperatures(temperature at the bottom) are in the range from 100 to 300° C. Thetemperature in the purification by distillation is preferably from 130to 250° C., particularly preferably from 150 to 220° C.

In a preferred embodiment of the invention, the purification bydistillation is carried out at a pressure of from 1 to 2000 mbar,preferably from 5 to 500 mbar, particularly preferably from 10 to 200mbar, and a temperature at the bottom of from 100 to 300° C., preferablyfrom 130 to 250° C., particularly preferably from 150 to 220° C.

If a column is used in the purification by distillation, the desiredproduct is preferably obtained via a side offtake. It is possible,according to the invention, to obtain the desired product in liquid orgaseous form. High boilers are preferably separated off at the bottom,and low boilers are preferably separated off at the top. If two columnsare used, the desired product preferably goes together with high boilersvia the bottom to the second column from which it can then be obtainedvia the top or once again as a side offtake stream. According to theinvention, it is also possible to use dividing wall columns.

It is also possible, according to the invention, for further treatmentsto be carried out between the individual steps of the process. Inparticular, it is possible according to the invention to separate offthe acid or the catalyst comprising at least one transition metal afterstep (di).

Before the distillation, extraction or crystallization in step (dii), itcan be advantageous to remove the acid or the catalyst comprising atleast one transition metal from the treated composition (C),particularly when the catalyst is present in homogeneously dissolvedform. In the case of heterogeneous acids or catalysts, this can beachieved, for example, by filtration, and in the case of homogeneousacids or catalysts, possible methods are, for example, extraction, forexample with water, or a distillation in which the acid is, depending onthe boiling point, separated off at the top or at the bottom and thecatalyst is preferably separated off at the bottom.

After the acid or the catalyst has been separated off, it canadvantageously be reused in step (di). According to the invention, it isalso possible for the acid or the catalyst to be subjected to anintermediate treatment, for example a purification, after it has beenseparated off and before it is reused in step (di).

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the acid or the catalyst comprising at leastone transition metal is separated off between the steps (di) and (dii).

In a preferred embodiment, the present invention therefore also providesa process as described above, wherein the acid is separated off afterstep (di) and is subsequently reused in step (di).

The treatment with acid or with a catalyst comprising at least onetransition metal is preferably carried out at temperatures of from 30 to350° C., for example from 60 to 350° C., in particular from 100 to 27°C., particularly preferably from 130 to 260° C.

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the treatment in step (di) is carried out ata temperature of from 60 to 350° C.

It has surprisingly been found that when compositions comprising atleast one cyclic ketone having from 7 to 16 carbon atoms are treatedwith acids or with a catalyst comprising at least one transition metal,cyclic ketones can be obtained in high yields and purities of above99.5% in a subsequent further purification, for example by distillation,extraction and/or crystallization. The cyclic ketone itself is notattacked or only very insignificantly attacked in the treatment.According to the invention, the compounds separated off are, inparticular, alcohols, aldehydes and epoxides.

Based on the cyclic ketone comprised in the composition, less than 10%of the ketone are lost according to the invention, preferably less than5%, in particular less than 3%.

The treatment in step (di) can be carried out either in the gas phase orin the liquid phase. The pressure can be set within a wide range. It canbe, for example, in the range from 0.001 to 300 bar, preferably from0.01 to 200 bar, particularly preferably from 0.1 to 100 bar. Accordingto the invention, preference is given to a pressure at which any lowboilers formed can be removed from the system by distillation, i.e. at apressure of from 0.25 to 70 bar, preferably from 0.35 to 50 bar,particularly preferably from 0.5 to 30 bar.

The treatment in step (di) can be carried out batchwise or continuously,with a continuous treatment being preferred. The residence times are,for example, in the range from 0.1 to 50 hours, preferably from 0.2 to24 hours, for example from 0.5 to 15 hours, in particular from 1 hour to19 hours, particularly preferably from 1.5 to 10 hours.

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein the treatment in step (di) is carried outfor a time of from 0.1 to 50 hours.

The acids used according to the invention are Bronsted or Lewis acids,with mixtures of two or more acids also being able to be used. The acidsused can be homogeneously dissolved or heterogeneous. Heterogeneousacids can, according to the invention, be used in suspended form or asfixed beds.

In a further embodiment, the present invention therefore also provides aprocess as described above, wherein the acid is in homogeneous orheterogeneous form.

The homogeneously soluble acids used according to the invention are, forexample, mineral acids or organic acids. Examples are sulfuric acid,sulfonic acids, nitric acid, hydrochloric acid, phosphoric acid,phosphorous acid, perchloric acid, heteropolyacids described in EP 0 158229 B1, C1 to C30 carboxylic acids such as formic acid, acetic acid,propionic acid, benzoic acid or the like.

Preferred homogeneous acids are phosphoric acid, phosphorous acid,sulfuric acid, sulfonic acids and heteropolyacids such astungstophosphoric acid. Particular preference is given to phosphoricacid and tungstophosphoric acid.

The content of homogeneously soluble acid is generally in the range from0.01 to 10% by weight, based on the cyclic ketone. Preference is givento using a homogeneously soluble acid in an amount of from 0.05 to 5% byweight, particularly preferably from 0.1 to 1% by weight.

In a preferred embodiment of the present invention, a homogeneouslysoluble acid is used in an amount of from 0.1 to 1% by weight.

After the cyclic ketone has been separated off by distillation, at leastpart of the acid is preferably recirculated to the treatment step.

Heterogeneous acids which are suitable for the purposes of the inventionare, for example, metal-oxidic solids which can, according to theinvention, have been treated with, for example, mineral acids such asphosphoric acid or sulfuric acid to increase their acid strength.Preference is given to using oxides or mixed oxides of B, Al, Si, Sn,Ti, Cr, Zr, Fe and Zn, which may comprise further constituents. Examplesof suitable oxidic compounds are zirconium oxide, titanium oxide,aluminum oxide, silicon oxide and combinations thereof, e.g.aluminosilicates such as zeolites. It is possible to use, for example,sheet silicates or natural clay minerals. It is likewise possible to useheterogeneous acids having an organic base, e.g. acid ion exchangers.

If the process of the invention using heterogeneous acids is carried outbatchwise, use is generally made of from 0.1 to 50% by weight of acid,based on the cyclic ketone. Preference is given to using a heterogeneousacid in an amount of from 0.5 to 20% by weight, particularly preferablyfrom 1 to 10% by weight.

If the process is carried out continuously using a heterogeneous acid, athroughput over the catalyst, i.e. the space velocity over theheterogeneous acid, of from 0.01 to 10 kg of cyclic ketone/liter ofcatalyst×h is preferably set. In particular, a space velocity over thecatalyst of from 0.05 to 2 kg of cyclic ketone/liter of catalyst×h,particularly preferably from 0.1 to 1 kg of cyclic ketone/liter ofcatalyst×h, is set.

In a preferred embodiment, the present invention therefore provides aprocess as described above, wherein a heterogeneous acid is used at aspace velocity over the catalyst of from 0.01 to 10 kg of cyclicketone/liter of catalyst×h.

The catalysts used according to the invention comprise at least onetransition metal, with catalysts comprising two or more transitionmetals or mixtures of two or more catalysts comprising at least onetransition metal also being able to be used. The catalysts used can behomogeneously dissolved or heterogeneous. Heterogeneous catalysts can,according to the invention, be used in suspended form or as fixed beds.

In a further embodiment, the present invention therefore also provides aprocess as described above, wherein the catalyst comprising at least onetransition metal is in homogeneous or heterogeneous form.

As catalysts comprising at least one transition metal, it is possible touse all customary catalysts in the process of the present invention.Possible transition metals are in principle all transition metals knownto those skilled in the art.

The homogeneously soluble catalysts used according to the invention aredescribed, for example, in Houben-Weyl, Methoden der Organischen Chemie,Volume IV/1c, pp. 45-67, Thieme Verlag Stuttgart, 1980.

Preferred homogeneous catalysts comprise Ru, Rh and/or Pd as transitionmetal. Particular preference is given to Ru.

The content of homogeneously soluble catalyst is generally in the rangefrom 0.001 to 1% by weight, based on the cyclic ketone. Preference isgiven to using a homogeneously soluble catalyst in an amount of from0.005 to 0.5% by weight, particularly preferably from 0.01 to 0.1% byweight.

In a preferred embodiment of the present invention, a homogeneouslysoluble catalyst is used in an amount of from 0.01 to 0.1% by weight.

After the cyclic ketone has been separated off by distillation, at leastpart of the catalyst is preferably recirculated to the treatment step(di).

Heterogeneous catalysts which are suitable according to the inventionare described, for example, in Houben-Weyl, Methoden der OrganischenChemie, Volume IV/1c, pp. 16-26, Thieme Verlag Stuttgart, 1980. Theycomprise at least one transition metal. Preferred transition metals areNi, Cu, Pd, Ru, Ir, Pt, Co and/or Rh. Particular preference is given toPd, Ru, Pt, and very particular preference is given to Ru and Pd.

The heterogeneous catalysts can be used in suspended form or preferablyin the form of a fixed bed. The catalysts comprising at least onetransition metal can comprise the transition metal as element or in theform of a chemical compound, for example as oxide. Mixtures of varioustransition metals can comprise the elements or their compounds asmixtures or as alloys. It is also possible to use elements which are nottransition metals or compounds thereof as catalyst components, forexample in Raney catalysts in which, for example, Al or aluminum oxideis used, preferably together with Ni, Cu or Ru.

Further examples of heterogeneous catalysts which are suitable for thepurposes of the invention are Ru on aluminum oxide, silicon oxide,titanium oxide, zirconium oxide, barium oxide, calcium oxide, Ru onactivated carbon, Pd on aluminum oxide, silicon oxide, titanium oxide,zirconium oxide, barium oxide, calcium oxide, Pd on activated carbon, Pton aluminum oxide, silicon oxide, titanium oxide, zirconium oxide,barium oxide, calcium oxide and Pt on activated carbon. As supportmaterials, it is also possible to use mixtures or compounds of variousmaterials, for example clay minerals or zeolites.

The catalyst used in the hydrogenation, for example, is also suitableaccording to the invention.

The catalysts comprising at least one transition metal can, according tothe invention, also have been applied to a support. The supports are,for example, metal-oxidic, basic, neutral or acidic solids which,according to the invention, may have been treated with mineral acidssuch as phosphoric acid or sulfuric acid to increase the acid strength.Preference is given to using oxides or mixed oxides of B, Al, Si, Sn,Ti, Cr, Zr, Fe and Zn, which can comprise further constituents. Examplesof suitable supports are zirconium oxide, titanium oxide, aluminumoxide, silicon oxide and combinations thereof, e.g. aluminosilicatessuch as zeolites. It is also possible to use, for example, sheetsilicates or natural clay minerals.

If the process of the invention using heterogeneous catalysts is carriedout batchwise, use is generally made of from 0.1 to 50% by weight ofcatalyst, based on the cyclic ketone. Preference is given to using aheterogeneous catalyst in an amount of from 0.5 to 20% by weight,particularly preferably from 1 to 10% by weight.

If step (di) of the process is carried out continuously using aheterogeneous catalyst, a throughput over the catalyst, i.e. the spacevelocity over the heterogeneous catalyst, of from 0.01 to 10 kg ofcyclic ketone/liter of catalyst×h is preferably set. In particular, aspace velocity over the catalyst from 0.05 to 2 kg of cyclicketone/liter of catalyst×h, particularly preferably from 0.1 to 1 kg ofcyclic ketone/liter of catalyst×h, is set.

In a preferred embodiment, the present invention therefore provides aprocess as described above, wherein a heterogeneous catalyst is used instep (d) at a space velocity over the catalyst from 0.01 to 10 kg ofcyclic ketone/liter of catalyst×h.

According to the invention, it is also possible for the acid or thecatalyst comprising at least one transition metal to be separated off instep (dii). However, it is likewise possible. for the purposes of thepresent invention, for the acid or the catalyst to be separated offafter step (di) and before step (dii). Possible methods of separationare, for example, distillation, extraction, precipitation orcrystallization.

In a further embodiment, the present invention therefore also provides aprocess as described above, wherein at least part of the acid or thecatalyst comprising at least one transition metal is separated off afterstep (di) and before step (dii).

In the process of the present invention, it is possible for at least oneintermediate treatment to be carried out between the steps (a) and (b)or between the steps (b) and (c) or between the steps (c) and (d) orbetween the steps (a) and (b) and (b) and (c) and (c) and (d). Forexample, it is possible for unreacted starting material or by-productsto be removed completely or partly in the intermediate treatment. If anintermediate treatment of the composition (A) is carried out after step(a), this gives, according to the invention, a composition (A′) which isthen used in step (b). It is likewise possible, according to theinvention, for an intermediate treatment of the composition (B) to becarried out after step (b), which then gives, according to theinvention, a composition (B′) which is then used in step (c). It islikewise possible, according to the invention, for an intermediatetreatment of the composition (C) to be carried out after step (c), whichthen gives, according to the invention, a composition (C′) which is thenused in step (d).

In a further embodiment, the present invention therefore also provides aprocess as described above for preparing a cyclic ketone having from 7to 16 carbon atoms, wherein unreacted starting material or by-productsare removed from the composition (A) after step (a) and before step (b)to give a composition (A′).

For the purposes of the invention, it is likewise possible for anintermediate treatment to comprise a plurality of different steps whichcan be identical or different.

Further possible intermediate treatments are, for example:

-   -   heating of the reaction mixture;    -   alteration of the pressure under which the reaction mixture is.        In this context, preference is given, for example, to increasing        the pressure by means of, for example, at least one pump and/or        at least one compressor;    -   introduction of at least one starting material. In particular,        solvents can be introduced.    -   Removal of product formed by means of at least one suitable        measure, for example preferably by means of at least one        distillation step.    -   Removal of unreacted starting material by means of at least one        suitable measure, for example preferably by means of at least        one distillation step.

The process of the invention gives a cyclic ketone in a purity of >95%,for example >98%, in particular >99%, determined by gas-chromatographicmethods. The cyclic ketone is preferably obtained in a purity of >99.5%,preferably >99.8%, particularly preferably >99.9%.

The combination according to the invention of a treatment with a base,in which aldehydes, in particular, are attacked, and treatment with anacid or a catalyst comprising transition metal, in which predominantlyepoxides and alcohols are attacked, gives particularly pure products. Atthe same time, the process of the invention is simple in terms ofapparatus and is inexpensive.

The present invention is illustrated below with the aid of examples.

EXAMPLES Comparative Example 1

The oxidation of 1,5,9-cyclododecatriene by means of N₂O and the work-upof the reaction product mixture were carried out in a manner analogousto Example 7 of WO 2005/030690.

The resulting distillate comprised 97% of cyclododeca-4,8-dienone andabout 2.8% of open-chain and cyclic aidehydes (4,8,11-dodecatrienal,cycloundecadiene carbaldehyde). 500 g of the distillate werehydrogenated over 50 ml of a 5% Pd/activated carbon catalyst at about120° C. and a hydrogen pressure of 30 bar for 5 hours in a 1 literautoclave. The catalyst was subsequently separated from thehydrogenation product by filtration at about 65° C. The product obtainedwas subsequently fractionally distilled at 10 mbar (absolute) via a 1 mpacked column comprising 5 mm metal mesh rings as packing elements.

75% of the distillation feed used was obtained as cyclododecanone havinga purity of 98.8%, 0.2% of unsaturated cyciododecanones, 0.4% ofcycloundecane carbaidehyde, 0.2% of dodecanal, 0.3% of dodecanol andtraces of further compounds were comprised as secondary components.

Example 2

1,5,9-Cyclododecatriene was oxidized by means of N₂O by the method ofExample 7 of WO 2005/030690, with unreacted 1,5,9-cyclododecatrienebeing separated off in a first column as described there. The bottomproduct from the first column had the following composition:cyclododeca-4,8-dienone (90% by weight), dodeca-4,8,11-trienal (2.2% byweight), cycloundeca-3,7-diene carbaldehyde (0.9% by weight) andcyclododecenedione (2.1% by weight). 550 g of this mixture were placedin a stirred flask and heated to 160° C. under protective gas (N₂). 2.75g of a 25% strength aqueous NaOH solution were subsequently added bymeans of a syringe. The reaction mixture remained clear and homogeneous.Samples were taken at regular intervals and analyzed by means of GC.After 35 minutes, the solution comprised only about 150 ppm by weight ofdodeca-4,8,11-trienal and 0.4% by weight of cycloundeca-3,7-dienecarbaldehyde. After 95 minutes, the solution comprised only about <30ppm by weight of dodeca-4,8,11-trienal and 760 ppm by weight ofcycloundeca-3,7-diene carbaldehyde.

The content of cyclododeca-4,8-dienone barely changed (88% by weightafter 95 minutes). The mixture was freed of high-boiling components in ashort path evaporator. 500 g of distillate were obtained.

Example 3

1,5,9-Cyclododecatriene was oxidized by means of N₂O and worked up bythe method of Example 7 of WO 2005/030690. It was distilled so that theoverhead product of the second distillation column had the followingcomposition: cyclododeca-4,8-dienone (98% by weight),dodeca-4,8,11-trienal (0.2% by weight) and cycloundeca-3,7-dienecarbaldehyde (0.7% by weight).

520 g of the overhead product were heated to 160° C. under a protectivegas atmosphere (N₂) in a stirred flask. 5.0 g of a 25% strength aqueousNaOH solution were subsequently added by means of a syringe. Thereaction mixture remained clear and homogeneous. Samples were taken atregular intervals and analyzed by means of GC. After 35 minutes, thesolution comprised less than 20 ppm by weight of dodeca-4,8,11-trienaland only about 0.2% by weight of cycloundeca-3,7-diene carbaldehyde.After 95 minutes, the solution comprised less than 10 ppm by weight ofdodeca-4,8,11-trienal and 400 ppm by weight of cycloundeca-3,7-dienecarbaldehyde. In contrast, the content of cyclododeca-4,8-dienone barelychanged (97% by weight).

Example 4

The 500 g of the distillate from Example 2 were hydrogenated over 50 mlof a 5% Pd/activated carbon catalyst at about 120° C. and a hydrogenpressure of 30 bar for 5 hours in a 1 liter autoclave. The catalyst wassubsequently separated off from the hydrogenation product by filtrationat about 65° C. The product was subsequently fractionally distilled at10 mbar (absolute) via a 1 m packed column comprising 5 mm metal meshrings as packing elements.

85% of the distillation feed used was obtained as cyclododecanone havinga purity of 99.8%. 0.03% of cycloundecane carbaldehyde, 0.01% ofdodecanol and traces of further compounds were comprised as secondarycomponents.

Example 5

Examples 2 and 4 were repeated with the difference that the filteredhydrogenation product was admixed with 1 g of 85% strength phosphoricacid and heated at 200° C. for 0.5 h. The mixture was subsequentlydistilled in a short path apparatus in order to separate the product offfrom the phosphoric acid. The short path distillate obtained wasdistilled as described in Example 2.

85% of the distillation feed used was obtained in a purity of 99.85%.Unsaturated cyclododecanones, cycloundecane carbaldehyde, dodecanal anddodecanol were no longer detectable in the product.

Example 6

The 500 g of the distillate from Example 2 were hydrogenated over 50 mlof a 5% Pd/activated carbon catalyst at about 120° C. and a hydrogenpressure of 30 bar for 5 hours in a 1 liter autoclave. The catalyst wassubsequently separated off from the hydrogenation product by filtrationat about 65° C. The product was then treated at 200° C. in the presenceof 20 g of TiO₂ for 1 hour, the titanium dioxide was subsequentlyfiltered off and the filtrate was subsequently fractionally distilled at10 mbar (absolute) via a 1 m packed column comprising 5 mm metal meshrings as packing elements.

90% of the distillation feed used was obtained as cyclododecanone havinga purity of 99.9%. Unsaturated cyclododecanones, cycloundecanecarbaldehyde, dodecanal and dodecanol were no longer detectable in theproduct.

1-13. (canceled)
 14. A process for preparing a cyclic ketone having from7 to 16 carbon atoms which comprises at least the steps (a) oxidizing acomposition (I) comprising at least one cyclic alkene which has from 7to 16 carbon atoms and at least one C—C double bond by means ofdinitrogen monoxide to give a composition (A), (b) treating thecomposition (A) with at least one base to give a composition (B), (c)hydrogenating the composition (B) in the presence of at least onecatalyst to give a composition (C), (d) purifying of the composition(C), comprising at least the steps (di) thermal treating the composition(C) with at least one acid or at least one catalyst comprising at leastone transition metal, (dii) further purifying by a method selected fromthe group consisting of distillation, extraction and crystallization.15. The process according to claim 14, wherein step (b) comprises thesteps (b1) and (b2): (b1) treating the composition (A) with at least onebase (b2) removing the base.
 16. The process according to claim 14,wherein the cyclic alkene has at least two C—C double bonds.
 17. Theprocess according to claim 14, wherein the cyclic alkene has three C—Cdouble bonds.
 18. The process according to claim 14, wherein unreactedstarting material or by-products are removed from the composition (A)after step (a) and before step (b) to give a composition (A′).
 19. Theprocess according to claim 14, wherein the acid or the catalystcomprising at least one transition metal is separated off between steps(di) and (dii).
 20. The process according to claim 14, wherein thecyclic alkene is 1,5,9-cyclododecatriene.
 21. The process according toclaim 14, wherein the cyclic alkene is cyclododecatriene which has beenprepared from butadiene by means of trimerization.
 22. The processaccording to claim 14, wherein the cyclic alkene is cyclododecene. 23.The process according to claim 14, wherein the base is sodium hydroxideor potassium hydroxide.
 24. The process according to claim 14, whereinthe treating in step (b) is carried out at a temperature of from 100 to250° C. for a period of from 1 minute to 10 hours.
 25. The processaccording to claim 14, wherein the treating in step (di) is carried outat a temperature of from 60 to 350° C.
 26. The process according toclaim 14, wherein the treating in step (di) is carried out for a time offrom 0.1 to 50 hours.
 27. A process for preparing a cyclic ketone havingfrom 7 to 16 carbon atoms which comprises at least the steps (a)oxidizing a composition (I) comprising at least one cyclic alkene whichhas from 7 to 16 carbon atoms and at least one C—C double bond by meansof dinitrogen monoxide to give a composition (A), (b) treating thecomposition (A) with at least one base to give a composition (B), (c)hydrogenating the composition (B) in the presence of at least onecatalyst to give a composition (C), (d) purifying of the composition(C), comprising at least the steps (di) thermal treating the composition(C) with at least one acid or at least one catalyst comprising at leastone transition metal, (dii) further purifuing by a method selected fromthe group consisting of distillation, extraction and crystallizationwherein step (b) comprises the steps (b1) and (b2): (b1) treatment ofthe composition (A) with at least one base (b2) removal of the base. 28.The process according to claim 27, wherein the acid or the catalystcomprising at least one transition metal is separated off between steps(di) and (dii).
 29. The process according to claim 27, wherein thecyclic alkene is cyclododecatriene which has been prepared frombutadiene by means of trimerization.
 30. The process according to claim28, wherein the cyclic alkene is cyclododecatriene which has beenprepared from butadiene by means of trimerization.
 31. The processaccording to claim 30, wherein unreacted starting material orby-products are removed from the composition (A) after step (a) andbefore step (b) to give a composition (A′).
 32. The process according toclaim 31, wherein the acid or the catalyst comprising at least onetransition metal is separated off between steps (di) and (dii).
 33. Theprocess according to claim 32, wherein the base is sodium hydroxide orpotassium hydroxide and the treating in step (b) is carried out at atemperature of from 100 to 250° C. for a period of from 1 minute to 10hours and the treating in step (di) is carried out at a temperature offrom 60 to 350° C. for a time of from 0.1 to 50 hours.